STEEL CASTINGS

DE-OXIDISING

DE-OXIDISING OF STEELS

CONTENT

1. DEFINITION
2. DE-OXIDISER
3. HOW DOES IT WORK?
4. REACTIONS
5. CHOICE OF THE DE-OXIDISER
6. RE-OXIDATION
7. CONCLUSION

1. DEFINITION
Is the addition to the melt, of an element or compound of elements, which reduces the level of
dissolved oxygen by the formation of oxides that are more stable than carbon monoxide.

The deoxidising must be done outside the mould, because otherwise the reaction-products,
being solid (possibly Al2O3), liquid (possibly MnO) or gaseous (possibly CO) remain in the
casting, giving a casting with gas inclusions, a "non conformity".

2. DE-OXIDISER
Any material, forming one or more oxide(s) that is (are) not reducible anymore by carbon at the
operating temperature.

This can be checked in the Ellingham diagram, figure on next page. The diagram is accurate
under the following conditions:

1. Equilibrium (molar concentrations),

2. Infinite time and
3. Constant temperature.

These conditions are never met in practice. But still the diagram is useful, because it gives an
indication of the relative oxidising tendency and the reaction-products formed.

All elements below the carbon monoxide line can be used; the lower in the diagram, the more
powerful they are. Combinations of elements can be more effective than adding the elements
separately.

Because unwanted effects can appear, each group of steels has a typical de-oxidiser or group
of de-oxidisers. Some examples are given in “Table 1” on page 3.
1

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

Figure Ellingham diagram

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

Table 1 De-oxidisers for steels

Material De-oxidiser

Carbon steel 0,1 % Al

Low alloyed steel 0,1 % Al + Ca
High chromium steel 0,05 % Al + Ca
Steel with risk for intergranular fracture Al + (Ca) + Ti or Zr

3. HOW DOES IT WORK?

3.1 Deoxidising should, to have the maximum effect, be done as late as possible.
The best is in the mould, because during the handling in the furnace, tapping,
transport, pouring and filling the mould, oxygen can dissolve in the metal, increasing
the oxygen-content.

The problems, to do it in the mould, will be:

* a non-homogeneous dispersion of the de-oxidiser

* an entrapment of reaction-products in the mould
* an incomplete dissolution of the de-oxidiser.

3.2 To overcome these problems, de-oxidising is mostly done during "tapping" with an extra
amount of de-oxidiser because of:

* re-oxidation in the time between tapping and solidification

* oxidation of the de-oxidiser itself.

3.3 The necessary amount is very difficult to calculate and depends on many factors: scrap,
returns, melting procedure, deslagging, holding time of the metal, tapping, ladle
practice, holding time in the ladle, pouring, mould material, pouring system...

Conclusion:

To have a good de-oxidation, two comments are important:

1. Each foundry has to establish and follow a "melting and pouring procedure", using a
specific de-oxidiser in a more are less constant quantity.

2. The result of the deoxidising must be continuously checked and eventually the type
and amount of de-oxidiser adapted to the results.

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

4. REACTIONS
The following items are very important:

1. During the cooling of the metal, the soluble amount of gases (N, H, O) decreases gradually,
with a sudden decrease during solidification. See figure below.

Figure Solubility of nitrogen and hydrogen in iron and steel

2. The oxides (result of the de-oxidation) have to float out of the metal, (after de-oxidation), but
if formed particles are

> 10 μm (SiO2) they will come easily to the surface

< 10 μm (Al2O3) they will probably not come out.

If there is some turbulence, they will be mixed with other non-metallic parts and come
out together with them.

3. During solidification, an interdendritic segregation of impurities will take place. The last
solidifying liquid will be enriched. To avoid the formation of carbon monoxide, there
must be, at this moment and the involved area, a sufficient amount of de-oxidiser
available.

4. If blowholes appear, caused by the gaseous CO, immediately the hydrogen and nitrogen
will diffuse towards them and stay there. If there is hydrogen and nitrogen present, the
necessary amount of silicon to prevent blowholes, is increasing. See figure below.
4

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

Figure

Formation of
Blowholes as a function
of
presence of
N and H

5. Important items to remember are:

* the faster the solidification, the better the inclusion control

* the design of the casting should be so that an easy removal or flowing out of the de-
oxidation products is possible
* thin walled castings will have problems, because the de-oxidation products will stick
to the mould walls
* a reaction with the mould material, containing S, H2O... can cause:

1. a "loss of de-oxidiser" necessary for purifying the metal

2. a casting surface with a low quality.

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

5. CHOICE OF THE DE-OXIDISER

5.1 Preliminary remark

5.2 Manganese
5.3 Silicon
5.4 Aluminium
5.5 Titanium
5.6 Zirconium
5.7 Calcium
5.8 Magnesium
5.9 REM (Rare Earth Metals)
5.10 Others
Conclusion for some steels

5.1 PRELIMINARY REMARK

The best de-oxidiser in steel is hydrogen. But it forms water vapour, which is very dangerous.
Hydrogen as such is hard to remove and can cause the famous hydrogen brittleness.

Carbon is also a good de-oxidiser, forming carbon monoxide gas (CO). But it is not used as a
de-oxidiser because a loss of carbon is not wanted.

In preference, de-oxidisers forming liquid or even more preferable, solid reaction-products are
chosen.

5.2 MANGANESE (Mn)

Manganese has the following features:

* It has a very low tendency to form oxides

* It is sometimes used as a supplement with other elements (Si, Al...)

* It has an additional effect in the formation of MnS, in preference above FeS

* It is added as ferromanganese (65-75 % Mn and for C are many possibilities), silico-

manganese (65-75 % Mn / 14-25 % Si) or calcium-silico-manganese (15-25 %
Mn / 15-25 % Ca / 40-60 % Si)

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

5.3 SILICON (Si)

This element is always present in steel. In cast steel there is a higher amount compared to
rolled steel. The following features are important:

* It has a low tendency to de-oxidise the metal. But its effect is sometimes sufficient to
prevent pinholes (see figure below).

Figure Pinholes in function of carbon and silicon

* It forms large inclusions. In combination with manganese it can form a liquid silicate,
which are fairly easy to remove.

* It reacts exothermic (increase of temperature).

* It is added as:

FeSi (45 to 75 % Si)

SiMn (14-25 % Si / 65-76 % Mn)
SiCr (40-47 % Si / 37-39 % Cr / 0,05 % C)
CaSi (60-65 % Si / 33-36 % Ca)
CaSiMn (40-60 % Si / 15-25 % Ca / 15-25 % Mn)
CaSiMg (30-40 % Si / 25-35 % Ca / 17-20 % Mg)

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

5.4 ALUMINIUM (Al)

Aluminium is the most frequently used de-oxidiser for carbon and low alloyed steels.
The features to remember are:

* It has a very high tendency to de-oxidise steel

* It is added as:

+ pure aluminium is a very light metal (2,7 kg / dm3) that is put in the tap stream
or on the bottom of the ladle (30-35 % recovery), or is plunged in metal,
fixed on a stick

+ remelted Al (This can contain unwanted elements as are zinc and copper)

+ ferro-aluminium (35 - 40 % Al) has a higher density (+/- 5,0 kg / dm3) and
requires more time to dissolve

* some other effects are:

1. a change of the sulphide morphology
2. a formation of clusters of aluminium
3. a formation of aluminium nitrides

1. Sulphide morphology

* the following typical sulphides exist:

+ type I with a globular form.

This type mostly exists with low levels of aluminium and has little
effect on the shock resistance test and reduction of area.
+ type II with an elongated form.
This type exists mostly with higher levels of aluminium. There is a
critical amount at which the shock resistance will drop to 10 % of
the normal value, the reduction of area to 40 %.
If it is used in combination with zirconium, this type of sulphides
will be formed.
+ type III with angular form.
This type exists mostly with very high levels of aluminium or
zirconium. The shock resistance can drop to 80 % of his original
value, the reduction of area to 90 %.
+ type IV with galaxies of sulphides.
This type exists if a large amount of REM's is present in the
metal.

So type II is very unwanted, type III can be tolerated, type I is the best, but
very difficult to obtain.

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

* why do they appear?

1. depending on aluminium content

kind of steel Amount of sulphides present

type I II III

low carbon 0,001-0,010 % 0,012-0,100 % 0,060-0,300 %

medium carbon 0,001-0,006 0,005-0,020 0,015-0,400
high carbon 0,001-0,005 0,005-0,030 0,020-0,300
plain carbon, 0,04Si 0,001-0,010 0,006-0,400 0,015-0,300
medium manganese 0,001-0,003 0,002-0,004 0,004-1,000
0,060-0,600

2. depending on the oxygen level

This is "the" determining factor for the shape of sulphur inclusions.

1. O2 > 0,02 % type I + oxides and or silicates

2. 0,01 < O2 < 0,02 % type I and II together
3. O2 < 0,01 % type II

3. depending on the amount of sulphur, eventually increasing in the

segregation zones during solidification.

* aluminium in presence of C and Si can promote type III

* the higher the cooling rate and the lower the aluminium content, the higher the
tendency to form type II. To overcome this, and to produce type III, there is a
need for more aluminium.
* the best effect is given by lowering the sulphur-content as much as possible by the
use of low sulphur-scrap and or by gas-bubbling and or another refining
techniques.

2. Alumina clusters

These are mostly found along the dendrites, where the metal was solidifying the last.

3. Aluminium nitrides

* These nitrides precipitate at the grain boundaries, promoting intergranular

fracture (rock candy fracture)

* They are present as dendritic or plate-like precipitates

* The presence of sulphur inclusions, type I and III, increase the fracture-susceptibility
due to aluminium-nitrides.

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

CONCLUSION

The aluminium content in steel should be:

+ higher than the level which forms porosity and type II sulphides
+ lower than the level which introduces intergranular fracture due to aluminium-
nitrides.

Mostly it will be in the range 0,04 - 0,07 % and for thick walled castings 0,03 - 0,05 %.

The use of aluminium is very often combined with titanium (Ti) and or zirconium (Zr) in order to
produce a better, less harmful nitride-formation.

5.5 TITANIUM (Ti)

Generally can be said that it:

+ is not as effective as aluminium as de-oxidiser. But it is a better nitride-former.

+ will decrease the impact value by +/- 80 % and increase the transition temperature
by 10 to 15 °C, compared to the effect by using aluminium.
+ does effect the sulphur-inclusions. But too high levels do not result in type II
formation
+ can promote carbides
+ can form a oxide-layer on the surface of the liquid metal, which affect the fluidity and
surface appearance

Titanium is used if:

+ the aluminium content is restricted

+ we want to avoid intergranular fracture (nitride builder)
+ we want to stabilise stainless steel by forming titanium-carbides to prevent the
formation of chromium-carbides and as a consequence, intergranular corrosion
+ in combination with other deoxidisers.

It is mostly used in the form of ferro-titanium (FeTi with +/- 80 % Ti)

The quantity is depending on the target. So is

+ 0,1 % Ti giving a residual level of 0,06-0,08 % Ti in a steel

+ titanium stabilising a stainless steel if % Ti > 5 x % C but < 0,70 %

10

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

5.6 ZIRCONIUM (Zr)

In general it can be said that zirconium is:

+ as effective de-oxidiser as aluminium, but more expensive

+ as effective as titanium concerning nitride-forming
+ incompetent to form a oxide-layer
+ better than titanium to avoid type II sulphides

The steel will have a lower impact value (+/- 80 %) and a higher transition temperature
(+10 to 15 °C) compared to steel that is de-oxidised with aluminium.

It is available as ferro-zirconium (FeZr) in the composition:

12 - 15 % Zr / 39 - 43 % Si / 0,2 % C or
35 - 40 % Zr / 47 - 52 % Si / 0,5 % C.

It is added in the tapping stream, after deoxidising with another element.

The preferred quantity is such that the residual level (after de-oxidising) is 0,03 - 0,10 %.

5.7 CALCIUM (Ca)

In general can be said that calcium:

+ is a most effective de-oxidiser, giving very stable oxides

+ has a very low melting and vapour point, so it is difficult to keep it in solution
+ has a very low efficiency if it is not added very deep in the metal, bubbling upwards
+ forms type I sulphides
+ its effect is more apparent in carbon steel than in a quenched + tempered low alloy
steel
The shock resistance of the steel drops to a level of 50 to 70 %, compared to
aluminium killed steel.

It is available as:

+ CaC : very effective but there is a carbon pick up

+ Inocal 10 : 5,4 % Ca/ 0,2 % C/ 0,6 % Si/ 0,15 % Fe/ balance Ni
+ Calsibar : 10-13 % Ca/ 9-12 % Ba/ 30-40 % Si/ 19-21 % Al/ balance Fe
Hypercal (lower reactivity)
+ SiCa : 33-36 % Ca/ 60-65 % Si
+ CaSiMn : 15-25 % Ca/ 40-60 % Si/ 12-25 % Mn

It is plunged in the metal or added in the tapping stream. The best way is to inject it in the ladle.
It gives more slag than the de-oxidising with aluminium.

11

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

5.8 MAGNESIUM (Mg)

In general can be said that magnesium:

+ is a strong de-oxidiser
+ has a restricted use because of its high vapour pressure and violent boiling
reaction. The lower the Mg-content, the less violent the reaction will be.
+ is also a good de-sulphuriser

It is available as:

+ FeSiMg : 4,8 % Mg / 60-70 % Si

+ CaSiMg : 17-20 % Mg / 25-30 % Ca / 35-40 % Si
+ several NiMg grades

MgO-slag combined with CaO will give a very dangerous slag, sticking at the
ladle lining, possibly going into the mould the next pouring.

The quantity used as a final de-oxidiser or as an extra element for nitrogen-removal can be 0,2
% nickel-magnesium (NiMg) or 0,3 to 0,4 % ferro-siliconmagnesium (FeSiMg).
It must be plunged below the surface in the ladle or even better injected in the ladle.

5.9 REM (RARE EARTH METALS)

These elements belong to the “Lanthanon group”: La, Ce, Pr, Nd, Pm, Eu, Gd, Tb... It are very
expensive elements.

They are better as de-oxidiser compared to silicon but weaker compared to aluminium.
They are strong de-oxidisers and de-sulphurisers. But it can be a problem to remove the
formed sulphides, which can give defects in the casting.

The REM's can react with the mould material (especially sulphur and oxygen), that mostly
gives a bad casting surface.

REM’s favour type I sulphides. But if too much is added, type IV sulphides can be formed
which forms a dirty metal and decrease the ductility.

If they are correctly used, the shock resistance at low temperatures will increase.

They are available as ferro-alloy FeCe, FeLa, FeSiCe,... These are added, mostly in the ladle,
after de-oxidising with aluminium.

12

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

The quantity to add can be calculated as follows:

+ Minimum REM = 5,85 (Oin - Ores) + 2,93 (Sin - Sres) + REMres

index "in" means initial value,

Index "rest" means rest-value (remaining value)

+ The monograph below is usable.

13

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

Another rules says to add 0,20 - 0,25 % of "Inchmeal", a naturally founded mixture of about
50-55 % Coe / 23-27 % La / 10-14 % Ned / 4-7 % Pr / other 1-2 %.

If Cerium and Lanthanum is added, the rule is:

1,0 % S < Ce + La < 1,6 % S

5.10 OTHERS

These are: Sodium (atrium-combination), Bad, K (potassium), and Li.

Most of them are good de-oxidisers and desulphurisers.

They are not solvable in steel.

They have a restricted use because of the explosive type of reaction, also giving irritating
alkaline fumes.

14

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

5.11 CONCLUSION

* Relative effect:

In next figure: the relative effect and affinity

of the different de-oxidisers is shown.

* Relative affinity to:

Carbon Nitrogen Oxygen Sulphur

Products: carbides nitrides oxides sulphides

Al weak very strong very strong weak

V strong very strong weak weak
Nb strong medium weak weak
Ti strong very strong very strong strong
Zr strong very strong very strong strong
REM weak strong very strong very strong

* Possible de-oxidisers are listed in the Addendum, included melting temperature and specific
weight.

General quantity:

0,1 to 0,3 % of pure element (as ferro-alloy more)

15

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

Quantity for “carbon and low alloyed steel”:

1. 0,1 % Al with residual levels of

0,04 to 0,08 % for thin to medium sections
0,03 to 0,05 % for thick sections (+ other de-oxidisers)

2. 0,3 % CaSi or CaSiMn

3. 0,1 % Al + 0,1 % Ti (as FeTi) or Zr (as SiZr)

first Al then Ti, Zr to prevent sulphur-problems and intergranular fracture

The exact quantity is depending on the content of O, N, H.

Quantity for “high chromium steel”:

1. Cr is a de-oxidiser itself, but is unable to pick up the oxygen during tapping and
pouring (lack of time)

2. Al gives aluminium-combinations that affect the surface finish and can

promote intergranular fracture

3. Si and Mn together, to form liquid manganese-silicates

4. Ca is the best but the working time is not long

Mostly one of the following possibilities is used:

+ 0,05 % Al and later 0,15 % Ca as CaSiMn or CaSi

+ 0,2 % Ca as CaSi or CaSiMn

Sometimes FeSiMg, NiMg, FeTi or REM are used.

16

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

6. RE - OXIDATION

This re-oxidation is possible because of the presence of:

1. air
2. moisture
3. iron oxides in magnesite linings, so that the end-level is even higher than the
original level.
4. alumina clusters in combination with magnesite
5. ladle lining, which cannot be magnesite
It produces duplex oxides as inclusions, for example:
Mn reduce SiO2 to MnO resulting at the end in
MnO.Al2O3.SiO complexes.

To reduce this the Mn/Si ratio must be as low as possible.

17

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

7. CONCLUSION

7.1 Al is the most common de-oxidiser, put in the metal:

plunged at the end of a rod when 50 % is tapped
added in the tapping stream when 30 % is tapped.

7.2 Too much Al gives intergranular fracture, especially in heavy section castings. A close
control of the N-content, also in the mould-material, is very important.

7.3 Too small amount of Al gives porosity and or type II sulphides. These are very harmful
and unwanted

7.4 Best residual Al content is:

0,04 - 0,07 %
0,03 - 0,05 % thick wall castings

7.5 Al can be combined with other de-oxidisers for specific reasons

Ti with residual level of 0,06-0,08 %

Zr with residual level of 0,03-0,10 % to avoid nitrite-problems

Zr gives a cleaner steel and better ductility at low temperatures

0,1 % Ca, added as 0,3 % CaSi or CaSiMn gives the best shock-resistance values

REM added after Al, is very effective

7.6 Remove the de-oxidation products!!!

* hold the metal some time after bringing in the de-oxidiser

* remove the de-oxidation products with a slag-coagulant, a deslagging powder suited
to the furnace- and ladle-lining.

7.7 To avoid the re-oxidation as much as possible:

+ pour as quick as possible

+ do not pour too many moulds with the same tap
+ do not use long runners
+ do use more ingates, especially for thin walled parts

7.8 The refractory attack of furnace and ladle is the highest if the steel is de-oxidised.
Therefore:

+ use clean ladles (no slag build up allowed)

+ use proper ladle-linings: pay attention with magnesite, alumina
+ do sinter the lining properly
+ do use the proper patching material and technique.
18

ir G HENDERIECKX GIETECH BV December 2004

 STEEL CASTINGS
DE-OXIDISING

ADDENDUM

De-oxidiser Melting point Specific weight

°C g / cm3

CaAl 700 - 960 2,6

CaSi 980 - 1200 2,5
CaSiAl 20 % Al 2,7
10 % Al 2,5

CaSiMn 3,4

FeMnSi very low carbon 1130 - 1235 5,8

low carbon 1075 - 1320 6,3

FeAl 30 - 40 % Al 1230 - 1270 5,2

+ / - 50 % Al 1160 - 1180 4,8

FeSi 75 75 % Si 1210 - 1315 2,8

FeSi 90 90 % Si 1210 - 1380 2,4

ZL 80 (FeSiZr) 1313 - 1345 2,7

SMZ (FeSiMnZr) 1105 - 1265 3,6

CaSiZr 3,3

CaSiMg 1000 - 1250 2,4

FeSiMg 5 950 - 1275 4,3

FeSiMg 10 940 - 1245 3,8

FeNiMg 1050 - 1070 6,0

NiMg 1050 - 1130 6,1

19

ir G HENDERIECKX GIETECH BV December 2004